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METHOD 13A - DETERMINATION OF TOTAL FLUORIDE EMISSIONS


FROM STATIONARY SOURCES
(SPADNS ZIRCONIUM LAKE METHOD)

NOTE: This method does not include all of the

specifications (e.g., equipment and supplies) and procedures

(e.g., sampling and analytical) essential to its

performance. Some material is incorporated by reference

from other methods in this part. Therefore, to obtain

reliable results, persons using this method should have a

thorough knowledge of at least the following additional test

methods: Method 1, Method 2, Method 3, and Method 5.

1.0 Scope and Application.

1.1 Analytes.
Analyte CAS No. Sensitivity
Total fluorides
as Fluorine 7782-41-4 Not determined

1.2 Applicability. This method is applicable for the

determination of fluoride (F-) emissions from sources as

specified in the regulations. It does not measure

fluorocarbons, such as Freons.

1.3 Data Quality Objectives. Adherence to the

requirements of this method will enhance the quality of the

data obtained from air pollutant sampling methods.

2.0 Summary.

Gaseous and particulate F- are withdrawn

isokinetically from the source and collected in water and on


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a filter. The total F- is then determined by the SPADNS

Zirconium Lake Colorimetric method.

3.0 Definitions. [Reserved]

4.0 Interferences.

4.1 Chloride. Large quantities of chloride will

interfere with the analysis, but this interference can be

prevented by adding silver sulfate into the distillation

flask (see Section 11.3). If chloride ion is present, it

may be easier to use the specific ion electrode method of

analysis (Method 13B).

4.2 Grease. Grease on sample-exposed surfaces may

cause low F- results due to adsorption.

5.0 Safety.

5.1 Disclaimer. This method may involve hazardous

materials, operations, and equipment. This test method may

not address all of the safety problems associated with its

use. It is the responsibility of the user of this test

method to establish appropriate safety and health practices

and to determine the applicability of regulatory limitations

prior to performing this test method.

5.2 Corrosive Reagents. The following reagents are

hazardous. Personal protective equipment and safe

procedures are useful in preventing chemical splashes. If

contact occurs, immediately flush with copious amounts of


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water at least 15 minutes. Remove clothing under shower and

decontaminate. Treat residual chemical burn as thermal

burn.

5.2.1 Hydrochloric Acid (HCl). Highly toxic. Vapors

are highly irritating to eyes, skin, nose, and lungs,

causing severe damage. May cause bronchitis, pneumonia, or

edema of lungs. Exposure to concentrations of 0.13 to 0.2

percent can be lethal in minutes. Will react with metals,

producing hydrogen.

5.2.2 Sodium Hydroxide (NaOH). Causes severe damage

to eye tissues and to skin. Inhalation causes irritation to

nose, throat, and lungs. Reacts exothermically with limited

amounts of water.

5.2.3 Sulfuric Acid (H2SO4). Rapidly destructive to

body tissue. Will cause third degree burns. Eye damage may

result in blindness. Inhalation may be fatal from spasm of

the larynx, usually within 30 minutes. May cause lung

tissue damage with edema. 1 mg/m3 for 8 hours will cause

lung damage or, in higher concentrations, death. Provide

ventilation to limit inhalation. Reacts violently with

metals and organics.

6.0 Equipment and Supplies.

6.1 Sample Collection. A schematic of the sampling

train used in performing this method is shown in Figure


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13A-1; it is similar to the Method 5 sampling train except

that the filter position is interchangeable. The sampling

train consists of the following components:

6.1.1 Probe Nozzle, Pitot Tube, Differential Pressure

Gauge, Filter Heating System, Temperature Sensor, Metering

System, Barometer, and Gas Density Determination Equipment.

Same as Method 5, Sections 6.1.1.1, 6.1.1.3 through 6.1.1.7,

6.1.1.9, 6.1.2, and 6.1.3, respectively. The filter heating

system and temperature sensor are needed only when moisture

condensation is a problem.

6.1.2 Probe Liner. Borosilicate glass or 316

stainless steel. When the filter is located immediately

after the probe, a probe heating system may be used to

prevent filter plugging resulting from moisture

condensation, but the temperature in the probe shall not be

allowed to exceed 120 ± 14 EC (248 ± 25 EF).

6.1.3 Filter Holder. With positive seal against

leakage from the outside or around the filter. If the

filter is located between the probe and first impinger, use

borosilicate glass or stainless steel with a 20-mesh

stainless steel screen filter support and a silicone rubber

gasket; do not use a glass frit or a sintered metal filter

support. If the filter is located between the third and

fourth impingers, borosilicate glass with a glass frit

filter support and a silicone rubber gasket may be used.


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Other materials of construction may be used, subject to the

approval of the Administrator.

6.1.4 Impingers. Four impingers connected as shown

in Figure 13A-1 with ground-glass (or equivalent),

vacuum-tight fittings. For the first, third, and fourth

impingers, use the Greenburg-Smith design, modified by

replacing the tip with a 1.3-cm (1/2-in.) ID glass tube

extending to 1.3 cm (1/2 in.) from the bottom of the flask.

For the second impinger, use a Greenburg-Smith impinger with

the standard tip. Modifications (e.g., flexible connections

between the impingers or materials other than glass) may be

used, subject to the approval of the Administrator. Place a

temperature sensor, capable of measuring temperature to

within 1 EC (2 EF), at the outlet of the fourth impinger for

monitoring purposes.

6.2 Sample Recovery. The following items are needed

for sample recovery:

6.2.1 Probe-liner and Probe-Nozzle Brushes, Wash

Bottles, Graduated Cylinder and/or Balance, Plastic Storage

Containers, Funnel and Rubber Policeman, and Funnel. Same

as Method 5, Sections 6.2.1, 6.2.2 and 6.2.5 to 6.2.8,

respectively.
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6.2.2 Sample Storage Container. Wide-mouth,

high-density polyethylene bottles for impinger water

samples, 1 liter.

6.3 Sample Preparation and Analysis. The following

items are needed for sample preparation and analysis:

6.3.1 Distillation Apparatus. Glass distillation

apparatus assembled as shown in Figure 13A-2.

6.3.2 Bunsen Burner.

6.3.3 Electric Muffle Furnace. Capable of heating to

600 EC (1100 EF).

6.3.4 Crucibles. Nickel, 75- to 100-ml.

6.3.5 Beakers. 500-ml and 1500-ml.

6.3.6 Volumetric Flasks. 50-ml.

6.3.7 Erlenmeyer Flasks or Plastic Bottles. 500-ml.

6.3.8 Constant Temperature Bath. Capable of

maintaining a constant temperature of ±1.0 EC at room

temperature conditions.

6.3.9 Balance. 300-g capacity, to measure to ±0.5 g.

6.3.10 Spectrophotometer. Instrument that measures

absorbance at 570 nm and provides at least a 1-cm light

path.

6.3.11 Spectrophotometer Cells. 1-cm path length.

7.0 Reagents and Standards.


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Unless otherwise indicated, all reagents are to

conform to the specifications established by the Committee

on Analytical Reagents of the American Chemical Society,

where such specifications are available. Otherwise, use the

best available grade.

7.1 Sample Collection. The following reagents are

needed for sample collection:

7.1.1 Filters.

7.1.1.1 If the filter is located between the third

and fourth impingers, use a Whatman No. 1 filter, or

equivalent, sized to fit the filter holder.

7.1.1.2 If the filter is located between the probe

and first impinger, use any suitable medium (e.g., paper,

organic membrane) that can withstand prolonged exposure to

temperatures up to 135 EC (275 EF), and has at least 95

percent collection efficiency (<5 percent penetration) for

0.3 µm dioctyl phthalate smoke particles. Conduct the

filter efficiency test before the test series, using ASTM D

2986-71, 78, or 95a (incorporated by reference--see

§ 60.17), or use test data from the supplier's quality

control program. The filter must also have a low F- blank

value (<0.015 mg F-/cm2 of filter area). Before the test

series, determine the average F- blank value of at least

three filters (from the lot to be used for sampling) using


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the applicable procedures described in Sections 8.3 and 8.4

of this method. In general, glass fiber filters have high

and/or variable F- blank values, and will not be acceptable

for use.

7.1.2 Water. Deionized distilled, to conform to ASTM

D 1193-77 or 91, Type 3 (incorporated by reference--see §

60.17). If high concentrations of organic matter are not

expected to be present, the potassium permanganate test for

oxidizable organic matter may be deleted.

7.1.3 Silica Gel, Crushed Ice, and Stopcock Grease.

Same as Method 5, Sections 7.1.2, 7.1.4, and 7.1.5,

respectively.

7.2 Sample Recovery. Water, as described in

Section 7.1.2, is needed for sample recovery.

7.3 Sample Preparation and Analysis. The following

reagents and standards are needed for sample preparation and

analysis:

7.3.1 Calcium Oxide (CaO). Certified grade

containing 0.005 percent F- or less.

7.3.2 Phenolphthalein Indicator. Dissolve 0.1 g of

phenolphthalein in a mixture of 50 ml of 90 percent ethanol

and 50 ml of water.

7.3.3 Silver Sulfate (Ag2SO4).

7.3.4 Sodium Hydroxide (NaOH), Pellets.

7.3.5 Sulfuric Acid (H2SO4), Concentrated.


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7.3.6 Sulfuric Acid, 25 Percent (v/v). Mix 1 part of

concentrated H2SO4 with 3 parts of water.

7.3.7 Filters. Whatman No. 541, or equivalent.

7.3.8 Hydrochloric Acid (HCl), Concentrated.

7.3.9 Water. Same as in Section 7.1.2.

7.3.10 Fluoride Standard Solution, 0.01 mg F-/ml.

Dry approximately 0.5 g of sodium fluoride (NaF) in an oven

at 110 EC (230 EF) for at least 2 hours. Dissolve 0.2210 g

of NaF in 1 liter of water. Dilute 100 ml of this solution

to 1 liter with water.

7.3.11 SPADNS Solution [4,5 Dihydroxyl-3-

(p-Sulfophenylazo)-2,7-Naphthalene-Disulfonic Acid Trisodium

Salt]. Dissolve 0.960 ± 0.010 g of SPADNS reagent in 500 ml

water. If stored in a well-sealed bottle protected from the

sunlight, this solution is stable for at least 1 month.

7.3.12 Spectrophotometer Zero Reference Solution.

Add 10 ml of SPADNS solution to 100 ml water, and acidify

with a solution prepared by diluting 7 ml of concentrated

HCl to 10 ml with deionized, distilled water. Prepare

daily.

7.3.13 SPADNS Mixed Reagent. Dissolve 0.135 ± 0.005

g of zirconyl chloride octahydrate (ZrOCl2 8H2O) in 25 ml of

water. Add 350 ml of concentrated HCl, and dilute to 500 ml

with deionized, distilled water. Mix equal volumes of this


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solution and SPADNS solution to form a single reagent. This

reagent is stable for at least 2 months.

8.0 Sample Collection, Preservation, Storage, and

Transport.

8.1 Pretest Preparation. Follow the general

procedure given in Method 5, Section 8.1, except that the

filter need not be weighed.

8.2 Preliminary Determinations. Follow the general

procedure given in Method 5, Section 8.2, except that the

nozzle size must be selected such that isokinetic sampling

rates below 28 liters/min (1.0 cfm) can be maintained.

8.3 Preparation of Sampling Train. Follow the

general procedure given in Method 5, Section 8.3, except for

the following variation:

Assemble the train as shown in Figure 13A-1 with the filter

between the third and fourth impingers. Alternatively, if a

20-mesh stainless steel screen is used for the filter

support, the filter may be placed between the probe and

first impinger. A filter heating system to prevent moisture

condensation may be used, but shall not allow the

temperature to exceed 120 ± 14 EC (248 ± 25 EF). Record the

filter location on the data sheet (see Section 8.5).

8.4 Leak-Check Procedures. Follow the leak-check

procedures given in Method 5, Section 8.4.


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8.5 Sampling Train Operation. Follow the general

procedure given in Method 5, Section 8.5, keeping the filter

and probe temperatures (if applicable) at 120 ± 14 EC (248 ±

25 EF) and isokinetic sampling rates below 28 liters/min

(1.0 cfm). For each run, record the data required on a data

sheet such as the one shown in Method 5, Figure 5-3.

8.6 Sample Recovery. Proper cleanup procedure begins

as soon as the probe is removed from the stack at the end of

the sampling period. Allow the probe to cool.

8.6.1 When the probe can be safely handled, wipe off

all external particulate matter near the tip of the probe

nozzle, and place a cap over it to keep from losing part of

the sample. Do not cap off the probe tip tightly while the

sampling train is cooling down as this would create a vacuum

in the filter holder, thus drawing water from the impingers

into the filter holder.

8.6.2 Before moving the sample train to the cleanup

site, remove the probe from the sample train, wipe off any

silicone grease, and cap the open outlet of the probe. Be

careful not to lose any condensate that might be present.

Remove the filter assembly, wipe off any silicone grease

from the filter holder inlet, and cap this inlet. Remove

the umbilical cord from the last impinger, and cap the

impinger. After wiping off any silicone grease, cap off the

filter holder outlet and any open impinger inlets and


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outlets. Ground-glass stoppers, plastic caps, or serum caps

may be used to close these openings.

8.6.3 Transfer the probe and filter-impinger assembly

to the cleanup area. This area should be clean and

protected from the wind so that the chances of contaminating

or losing the sample will be minimized.

8.6.4 Inspect the train prior to and during

disassembly, and note any abnormal conditions. Treat the

samples as follows:

8.6.4.1 Container No. 1 (Probe, Filter, and Impinger

Catches).

8.6.4.1.1 Using a graduated cylinder, measure to the

nearest ml, and record the volume of the water in the first

three impingers; include any condensate in the probe in this

determination. Transfer the impinger water from the

graduated cylinder into a polyethylene container. Add the

filter to this container. (The filter may be handled

separately using procedures subject to the Administrator's

approval.) Taking care that dust on the outside of the

probe or other exterior surfaces does not get into the

sample, clean all sample-exposed surfaces (including the

probe nozzle, probe fitting, probe liner, first three

impingers, impinger connectors, and filter holder) with

water. Use less than 500 ml for the entire wash. Add the
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washings to the sample container. Perform the water rinses

as follows:

8.6.4.1.2 Carefully remove the probe nozzle and rinse

the inside surface with water from a wash bottle. Brush

with a Nylon bristle brush, and rinse until the rinse shows

no visible particles, after which make a final rinse of the

inside surface. Brush and rinse the inside parts of the

Swagelok fitting with water in a similar way.

8.6.4.1.3 Rinse the probe liner with water. While

squirting the water into the upper end of the probe, tilt

and rotate the probe so that all inside surfaces will be

wetted with water. Let the water drain from the lower end

into the sample container. A funnel (glass or polyethylene)

may be used to aid in transferring the liquid washes to the

container. Follow the rinse with a probe brush. Hold the

probe in an inclined position, and squirt water into the

upper end as the probe brush is being pushed with a twisting

action through the probe. Hold the sample container

underneath the lower end of the probe, and catch any water

and particulate matter that is brushed from the probe. Run

the brush through the probe three times or more. With

stainless steel or other metal probes, run the brush through

in the above prescribed manner at least six times since

metal probes have small crevices in which particulate matter

can be entrapped. Rinse the brush with water, and


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quantitatively collect these washings in the sample

container. After the brushing, make a final rinse of the

probe as described above.

8.6.4.1.4 It is recommended that two people clean the

probe to minimize sample losses. Between sampling runs,

keep brushes clean and protected from contamination.

8.6.4.1.5 Rinse the inside surface of each of the

first three impingers (and connecting glassware) three

separate times. Use a small portion of water for each

rinse, and brush each sample-exposed surface with a Nylon

bristle brush, to ensure recovery of fine particulate

matter. Make a final rinse of each surface and of the

brush.

8.6.4.1.6 After ensuring that all joints have been

wiped clean of the silicone grease, brush and rinse with

water the inside of the filter holder (front-half only, if

filter is positioned between the third and fourth

impingers). Brush and rinse each surface three times or

more if needed. Make a final rinse of the brush and filter

holder.

8.6.4.1.7 After all water washings and particulate

matter have been collected in the sample container, tighten

the lid so that water will not leak out when it is shipped

to the laboratory. Mark the height of the fluid level to


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transport. Label the container clearly to identify its

contents.

8.6.4.2 Container No. 2 (Sample Blank). Prepare a

blank by placing an unused filter in a polyethylene

container and adding a volume of water equal to the total

volume in Container No. 1. Process the blank in the same

manner as for Container No. 1.

8.6.4.3 Container No. 3 (Silica Gel). Note the color

of the indicating silica gel to determine whether it has

been completely spent, and make a notation of its condition.

Transfer the silica gel from the fourth impinger to its

original container, and seal. A funnel may be used to pour

the silica gel and a rubber policeman to remove the silica

gel from the impinger. It is not necessary to remove the

small amount of dust particles that may adhere to the

impinger wall and are difficult to remove. Since the gain

in weight is to be used for moisture calculations, do not

use any water or other liquids to transfer the silica gel.

If a balance is available in the field, follow the

analytical procedure for Container No. 3 in Section 11.4.2.


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9.0 Quality Control.

9.1 Miscellaneous Quality Control Measures.

Quality Control
Section Measure Effect
8.4, Sampling equipment Ensure accurate
10.1 leak-check and measurement of stack gas
calibration flow rate and sample
volume
10.2 Spectrophotometer Evaluate analytical
calibration technique, preparation of
standards
11.3.3 Interference/recovery Minimize negative effects
efficiency check of used acid
during distillation

9.2 Volume Metering System Checks. Same as Method 5,

Section 9.2.

10.0 Calibration and Standardization.

NOTE: Maintain a laboratory log of all calibrations.

10.1 Sampling Equipment. Calibrate the probe nozzle,

pitot tube, metering system, probe heater, temperature

sensors, and barometer according to the procedures outlined

in Method 5, Sections 10.1 through 10.6. Conduct the

leak-check of the metering system according to the

procedures outlined in Method 5, Section 8.4.1.

10.2 Spectrophotometer.

10.2.1 Prepare the blank standard by adding 10 ml of

SPADNS mixed reagent to 50 ml of water.

10.2.2 Accurately prepare a series of standards from

the 0.01 mg F-/ml standard fluoride solution (Section


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7.3.10) by diluting 0, 2, 4, 6, 8, 10, 12, and 14 ml to 100

ml with deionized, distilled water. Pipet 50 ml from each

solution, and transfer each to a separate 100-ml beaker.

Then add 10 ml of SPADNS mixed reagent (Section 7.3.13) to

each. These standards will contain 0, 10, 20, 30, 40, 50,

60, and 70 µg F- (0 to 1.4 µg/ml), respectively.

10.2.3 After mixing, place the blank and calibration

standards in a constant temperature bath for 30 minutes

before reading the absorbance with the spectrophotometer.

Adjust all samples to this same temperature before

analyzing.

10.2.4 With the spectrophotometer at 570 nm, use the

blank standard to set the absorbance to zero. Determine the

absorbance of the standards.

10.2.5 Prepare a calibration curve by plotting µg F-

/50 ml versus absorbance on linear graph paper. Prepare the

standard curve initially and thereafter whenever the SPADNS

mixed reagent is newly made. Also, run a calibration

standard with each set of samples and, if it differs from

the calibration curve by more than ±2 percent, prepare a new

standard curve.

11.0 Analytical Procedures.

11.1 Sample Loss Check. Note the liquid levels in

Containers No. 1 and No. 2, determine whether leakage


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occurred during transport, and note this finding on the

analytical data sheet. If noticeable leakage has occurred,

either void the sample or use methods, subject to the

approval of the Administrator, to correct the final results.

11.2 Sample Preparation. Treat the contents of each

sample container as described below:

11.2.1 Container No. 1 (Probe, Filter, and Impinger

Catches). Filter this container's contents, including the

sampling filter, through Whatman No. 541 filter paper, or

equivalent, into a 1500-ml beaker.

11.2.1.1 If the filtrate volume exceeds 900 ml, make

the filtrate basic (red to phenolphthalein) with NaOH, and

evaporate to less than 900 ml.

11.2.1.2 Place the filtered material (including

sampling filter) in a nickel crucible, add a few ml of

water, and macerate the filters with a glass rod.

11.2.1.2.1 Add 100 mg CaO to the crucible, and mix

the contents thoroughly to form a slurry. Add two drops of

phenolphthalein indicator. Place the crucible in a hood

under infrared lamps or on a hot plate at low heat.

Evaporate the water completely. During the evaporation of

the water, keep the slurry basic (red to phenolphthalein) to

avoid loss of F-. If the indicator turns colorless (acidic)

during the evaporation, add CaO until the color turns red

again.
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11.2.1.2.2 After evaporation of the water, place the

crucible on a hot plate under a hood, and slowly increase

the temperature until the Whatman No. 541 and sampling

filters char. It may take several hours to char the filters

completely.

11.2.1.2.3 Place the crucible in a cold muffle

furnace. Gradually (to prevent smoking) increase the

temperature to 600 EC (1100 EF), and maintain this

temperature until the contents are reduced to an ash.

Remove the crucible from the furnace, and allow to cool.

11.2.1.2.4 Add approximately 4 g of crushed NaOH to

the crucible, and mix. Return the crucible to the muffle

furnace, and fuse the sample for 10 minutes at 600 EC.

11.2.1.2.5 Remove the sample from the furnace, and

cool to ambient temperature. Using several rinsings of warm

water, transfer the contents of the crucible to the beaker

containing the filtrate. To ensure complete sample removal,

rinse finally with two 20-ml portions of 25 percent H2SO4,

and carefully add to the beaker. Mix well, and transfer to

a 1-liter volumetric flask. Dilute to volume with water,

and mix thoroughly. Allow any undissolved solids to settle.

11.2.2 Container No. 2 (Sample Blank). Treat in the

same manner as described in Section 11.2.1 above.

11.2.3 Adjustment of Acid/Water Ratio in Distillation

Flask. Place 400 ml of water in the distillation flask, and


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add 200 ml of concentrated H2SO4. Add some soft glass beads

and several small pieces of broken glass tubing, and

assemble the apparatus as shown in Figure 13A-2. Heat the

flask until it reaches a temperature of 175 EC (347 EF) to

adjust the acid/water ratio for subsequent distillations.

Discard the distillate.

CAUTION: Use a protective shield when carrying out

this procedure. Observe standard precautions when mixing

H2SO4 with water. Slowly add the acid to the flask with

constant swirling.

11.3 Distillation.

11.3.1 Cool the contents of the distillation flask to

below 80 EC (180 EF). Pipet an aliquot of sample containing

less than 10.0 mg F- directly into the distillation flask,

and add water to make a total volume of 220 ml added to the

distillation flask. (To estimate the appropriate aliquot

size, select an aliquot of the solution, and treat as

described in Section 11.4.1. This will be an approximation

of the F- content because of possible interfering ions.)

NOTE: If the sample contains chloride, add 5 mg of

Ag2SO4 to the flask for every mg of chloride.

11.3.2 Place a 250-ml volumetric flask at the

condenser exit. Heat the flask as rapidly as possible with

a Bunsen burner, and collect all the distillate up to 175 EC


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(347 EF). During heatup, play the burner flame up and down

the side of the flask to prevent bumping. Conduct the

distillation as rapidly as possible (15 minutes or less).

Slow distillations have been found to produce low F-

recoveries. Be careful not to exceed 175 EC (347 EF) to

avoid causing H2SO4 to distill over. If F- distillation in

the mg range is to be followed by a distillation in the

fractional mg range, add 220 ml of water and distill it over

as in the acid adjustment step to remove residual F- from

the distillation system.

11.3.3 The acid in the distillation flask may be used

until there is carry-over of interferences or poor F-

recovery. Check for interference and for recovery

efficiency every tenth distillation using a water blank and

a standard solution. Change the acid whenever the F-

recovery is less than 90 percent or the blank value exceeds

0.1 µg/ml.

11.4 Sample Analysis.

11.4.1 Containers No. 1 and No. 2.

11.4.1.1 After distilling suitable aliquots from

Containers No. 1 and No. 2 according to Section 11.3, dilute

the distillate in the volumetric flasks to exactly 250 ml

with water, and mix thoroughly. Pipet a suitable aliquot of

each sample distillate (containing 10 to 40 µg F-/ml) into a

beaker, and dilute to 50 ml with water. Use the same


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aliquot size for the blank. Add 10 ml of SPADNS mixed

reagent (Section 7.3.13), and mix thoroughly.

11.4.1.2 After mixing, place the sample in a

constant-temperature bath containing the standard solutions

for 30 minutes before reading the absorbance on the

spectrophotometer.

NOTE: After the sample and colorimetric reagent are

mixed, the color formed is stable for approximately 2 hours.

Also, a 3 EC (5.4 EF) temperature difference between the

sample and standard solutions produces an error of

approximately 0.005 mg F-/liter. To avoid this error, the

absorbencies of the sample and standard solutions must be

measured at the same temperature.

11.4.1.3 Set the spectrophotometer to zero absorbance

at 570 nm with the zero reference solution (Section 7.3.12),

and check the spectrophotometer calibration with the

standard solution (Section 7.3.10). Determine the

absorbance of the samples, and determine the concentration

from the calibration curve. If the concentration does not

fall within the range of the calibration curve, repeat the

procedure using a different size aliquot.

11.4.2 Container No. 3 (Silica Gel). Weigh the spent

silica gel (or silica gel plus impinger) to the nearest


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0.5 g using a balance. This step may be conducted in the

field.

12.0 Data Analysis and Calculations.

Carry out calculations, retaining at least one extra

significant figure beyond that of the acquired data. Round

off figures after final calculation. Other forms of the

equations may be used, provided that they yield equivalent

results.

12.1 Nomenclature.

Ad = Aliquot of distillate taken for color

development, ml.

At = Aliquot of total sample added to still, ml.

Bws = Water vapor in the gas stream, portion by

volume.

Cs = Concentration of F- in stack gas, mg/dscm

(gr/dscf).

Fc = F- concentration from the calibration curve,

µg.

Ft = Total F- in sample, mg.

Tm = Absolute average dry gas meter (DGM)

temperature (see Figure 5-3 of Method 5),

EK ( ER).

Ts = Absolute average stack gas temperature (see

Figure 5-3 of Method 5), EK ( ER).


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Vd = Volume of distillate as diluted, ml.

Vm(std) = Volume of gas sample as measured by DGM at

standard conditions, dscm (dscf).

Vt = Total volume of F- sample, after final

dilution, ml.

Vw(std) = Volume of water vapor in the gas sample at

standard conditions, scm (scf)

12.2 Average DGM Temperature and Average Orifice

Pressure Drop (see Figure 5-3 of Method 5).

12.3 Dry Gas Volume. Calculate Vm(std), and adjust for

leakage, if necessary, using Equation 5-1 of Method 5.

12.4 Volume of Water Vapor and Moisture Content.

Calculate Vw(std) and Bws from the data obtained in this

method. Use Equations 5-2 and 5-3 of Method 5.

12.5 Total Fluoride in Sample. Calculate the amount

of F- in the sample using the following equation:

K Vt V d Fc
Ft ' Eq. 13A-1
At Ad

where:

K = 10-3 mg/µg (metric units)

= 1.54 × 10-5 gr/µg (English units)

12.6 Fluoride Concentration in Stack Gas. Determine

the F- concentration in the stack gas using the following

equation:
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Ft
Cf ' Eq. 13A-2
Vm(std)

12.7 Isokinetic Variation. Same as Method 5,

Section 12.11.

13.0 Method Performance.

The following estimates are based on a collaborative

test done at a primary aluminum smelter. In the test, six

laboratories each sampled the stack simultaneously using two

sampling trains for a total of 12 samples per sampling run.

Fluoride concentrations encountered during the test ranged

from 0.1 to 1.4 mg F-/m3.

13.1 Precision. The intra- and inter-laboratory

standard deviations, which include sampling and analysis

errors, were 0.044 mg F-/m3 with 60 degrees of freedom and

0.064 mg F-/m3 with five degrees of freedom, respectively.

13.2 Bias. The collaborative test did not find any

bias in the analytical method.

13.3 Range. The range of this method is 0 to 1.4 µg

F-/ml.

14.0 Pollution Prevention. [Reserved]

15.0 Waste Management. [Reserved]

16.0 Alternative Procedures.


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16.1 Compliance with ASTM D 3270-73T, 80, 91, or 95

(incorporated by reference - see § 60.17) "Analysis of

Fluoride Content of the Atmosphere and Plant Tissues

(Semiautomated Method) is an acceptable alternative for the

requirments specified in Sections 11.2, 11.3, and 11.4.1

when applied to suitable aliquots of Containers 1 and 2

samples.
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17.0 References.

1. Bellack, Ervin. Simplified Fluoride Distillation

Method. J. of the American Water Works Association.

50:5306. 1958.

2. Mitchell, W.J., J.C. Suggs, and F.J. Bergman.

Collaborative Study of EPA Method 13A and Method 13B.

Publication No. EPA-300/4-77-050. U.S. Environmental

Protection Agency, Research Triangle Park, NC.

December 1977.

3. Mitchell, W.J., and M.R. Midgett. Adequacy of

Sampling Trains and Analytical Procedures Used for Fluoride.

Atm. Environ. 10:865-872. 1976.

18.0 Tables, Diagrams, Flowcharts, and Validation Data.


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Figure 13A-1. Fluoride Sampling Train.


872

Connecting Tube
12 mm ID
T 24
S
40

Thermometer

T 24
S
40

With
T 10
S 30 S 24
T
40
Adapter
Adapter

T 24
S
40

Condenser

1-Liter
Flask

500-ml
Erlenmeyer
Flask

Figure 13A-2. Fluoride Distillation Apparatus.


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